CN1258554C - Aqueous based dispersions of polyolefinic substrates - Google Patents
Aqueous based dispersions of polyolefinic substrates Download PDFInfo
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- CN1258554C CN1258554C CNB998165468A CN99816546A CN1258554C CN 1258554 C CN1258554 C CN 1258554C CN B998165468 A CNB998165468 A CN B998165468A CN 99816546 A CN99816546 A CN 99816546A CN 1258554 C CN1258554 C CN 1258554C
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- chlorinatedpolyolefins
- acrylic acid
- polymkeric substance
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/07—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Abstract
The present invention relates to stable aqueous dispersions of an acrylic modified chlorinated polyolefin and a process for their preparation. The aqueous dispersions of acrylic modified chlorinated polyolefin are effective for use as coatings on treated and untreated polyolefinic substrates.
Description
The present invention relates to be used for the stabilization of polymer aqueous dispersions of untreated polyolefin substrate with coating.Or rather, by in hydrophilic organic solvent, forming polymer salt, and from the mixture of water and hydrophilic organic solvent, remove hydrophilic organic solvent, prepare the aqueous dispersions of chlorinatedpolyolefins (CPO) polymkeric substance of acrylic acid or the like modification.
The background of invention
Because polyolefin resin for example polypropylene has satisfactory physicals and lower price, it is very extensive that their purposes becomes.Polyolefine material is widely used in automobile industry, makes various automotive interiors and outside part, for example collision bumper, side mirror support, inner panel board and door handle.Usually need to apply coating on the polyolefin substrate, to obtain for example protectiveness and/or ornamental coating.
Because coating is to the base material poor adhesive force of these types, so it is very difficult usually to be coated with untreated polyolefin substrate.Polypropylene has low surface tension and low polarity.Therefore, be difficult to guarantee that the coating that is applied is attached to the surface of polypropylene base effectively.
Acquisition is the material that makes base material carry out modification or use tackify to two kinds of methods of the sticking power of polyolefin substrate.The pre-treatment of base material generally includes by for example flame treating, plasma gas, corona discharge, UV-irradiation or chemical process and comes oxidized surface.There is the inhomogeneity problem of processing usually in these methods or can increases surfaceness or overheated and damage base material.Chlorinatedpolyolefins has been used as tackifier.It is believed that they can be attached on the base material by London force.Chlorine can improve the solubleness in all kinds of SOLVENTS, also increases the sticking power of priming paint to finish paint by polar interaction.
To the coating industry worry of the environment of aspect with an organic solvent, become serious day by day.This worry not only extends to the protection to environment self, and has extended to the public's security, as living and working conditions.By industry and the consuming public applies and the coating composition that uses in the organic volatile that produces not only usually be to make us uncomfortable, and impel the formation photo-chemical smog.Government has formulated rule, has set forth the standard about the organic volatile compound (VOC) that may discharge into the atmosphere.EPA (EPA) has been worked out the standard that limits the amount of the VOC that discharges into the atmosphere, and these standard plans allow the u s. state adopt or to have adopted.About the standard of VOCs for example EPA with environmental concerns especially with use the paint and the coating industry that can enter atmospheric organic solvent relevant.
Developed the watersoluble chlorinated polyolefin compositions of the priming paint that can be used as the painting polypropylene base material.The type composition requires to form the CPO emulsion usually.These emulsions generally comprise the solubility promoter in CPO, tensio-active agent, amine, water and some occasions of maleinization.EP774500 described in these emulsions a kind of and acrylic resin and can with the mixture of the linking agent of acrylic resin reaction aqueous coating system to provide untreated polypropylene to use.This system is mixture and the tensio-active agent that contains significant quantity.
United States Patent (USP) № 5,637,409 has described the water-based paint compositions of the mixture that contains tensio-active agent, CPO, monomer, solvent, amine and water.This dispersion is mixed with initiator, then on the paint base material.Then, monomer generation polymerization.This technology is actually two components system, contains undesirable stink and must be noted that monomeric processing.Such system makes that preparation zero defect uniform films is very difficult.
The general introduction of invention
The present invention relates to the stabilize water dispersion liquid and preparation method thereof of the chlorinatedpolyolefins of acrylic acid or the like modification.The aqueous dispersions of the chlorinatedpolyolefins of this acrylic acid or the like modification can be effectively with deal with untreated polyolefin substrate on coating.Aqueous dispersions of the present invention contains the organic solvent that is lower than about 10% (weight), at least about the solid of 10% (weight), and under about envrionment temperature, viscosity is lower than about 10 pools.Aqueous dispersions of the present invention can provide sticking power to record the coating that is at least 4B by ASTM method D3359 effectively.
In an importance of the present invention, weight-average molecular weight is at least about 1000 chlorinatedpolyolefins by carrying out modification with the acrylic acid or the like grafting.Preformed acrylic polymers can be grafted on the chlorinatedpolyolefins, or acrylic monomer can grafting and be aggregated on the chlorinatedpolyolefins.In an importance of the present invention, be grafted to the acrylic acid or the like on the chlorinatedpolyolefins, it or be grafted to preformed acrylic polymers on the chlorinatedpolyolefins, or acrylic monomer grafting and being aggregated on the chlorinatedpolyolefins, its weight-average molecular weight is at least about 2000.Acrylic acid or the like provides the chlorinatedpolyolefins that makes the acrylic acid or the like modification to form the ionogen of stabilize water dispersion liquid effectively for the chlorinatedpolyolefins of acrylic acid or the like modification.
According to dispersing method of the present invention, the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification synthesizes in organic solvent.Organic solvent can be the mixture of hydrophilic organic solvent, hydrophobic nature organic solvent or hydrophobic nature organic solvent and hydrophilic organic solvent.In an importance of the present invention, organic solvent is a hydrophilic organic solvent, and under processing temperature, the solubleness of hydrophilic solvent in water is at least about 5% (weight), is benchmark with the weight of the mixture of solvent and water.The acid number that is formed at the polymkeric substance in the organic solvent is at least about 10, and its solubleness in organic solvent under processing temperature is at least about 25% (weight), is benchmark with the weight of polymkeric substance and solvent.
Polymkeric substance is dissolved in after the organic solvent fully, can add in the neutralizing agent and polymkeric substance, and mode is to add polymkeric substance in the water that contains neutralizing agent, or Xiang Shuizhong adding polymkeric substance, adds neutralizing agent then in the mixture of polymkeric substance/water.According to the ionogen type that is present in the polymkeric substance, importantly with before water mixes in and polymkeric substance, the dispersible neutral ionogen of water can be distributed in the whole polymkeric substance usually equably.
In an importance of the present invention, the add-on of neutralizing agent is the amount that polymer dispersed can be provided when removing organic solvent effectively.Neutralizing agent can be any salifiable alkali of shape that can be compatible with ionizable functional polymer, for example sodium hydroxide or amine.One very important aspect, neutralizing agent is an amine, comprises ammonia, trolamine, dimethylethanolamine, diethylamine (DEA), triethylamine (TEA), 2-amino-2-methyl-1-propanol and composition thereof.Ionogen on the not every polymkeric substance all needs and alkali reaction (or neutralization).
In organic solvent, form after the polymer salt solution, this solution is mixed with water, form water/organic solvent/polymer salt blend, remove from blend or stripping organic solvent and possible a part of water under certain time limit, temperature and pressure, so that a kind of like this aqueous dispersions to be provided effectively, the resin median size that it contains is not more than about 15 microns, an importance, be not more than about 10 microns, one very important aspect, be not more than about 5 microns.In addition, remove after organic solvent and the water, the polymer concentration of aqueous dispersions is at least about 10% (weight), and the concentration of organic solvent is lower than about 10% (weight).
In the final step of the inventive method, organic solvent removes from water/organic solvent/polymer salt blend.Of the present invention one very important aspect in, under 25 ℃, the viscosity of formed dispersion liquid is lower than about 10 pools.
In another aspect of this invention, the temperature of stripping operation is lower than the temperature that neutralizing agent can otherwise lose in a large number.The median size of resin is no more than about more than 15 microns, and in an importance of the present invention, the average particle size range of dispersion liquid is for being lower than about 10 microns.Particle diameter is higher than about 15 microns dispersion liquid can not have qualified stability.
Detailed description of the invention
Definition
" polymer support " refers in the coatings formulated to be all polymkeric substance and resin Compositions before the film forming,, comprise and be not limited to the polymer salt that can be scattered in water.Polymer support can comprise linking agent.
" coating adhesive agent " refers to after the solvent evaporation and any possible crosslinked polymer moieties of the film of coating afterwards that all takes place.
" coatings formulated " refers to choose wantonly adding to give coatings formulated with satisfactory application characteristic with give film with satisfactory performance for example polymer support, solvent, pigment, catalyzer and the additive of opacity and color.
" water medium " used herein speech refer to water and wherein water-content be at least the water of 10% (weight) and the mixture of hydrophilic organic solvent.The example of hydrophilic solvent comprises alkyl alcohol, for example Virahol, methyl alcohol, ethanol, n-propyl alcohol, propyl carbinol, sec-butyl alcohol, the trimethyl carbinol and isopropylcarbinol; Ether alcohol, for example methylcyclohexane, ethyl cellosolve, propyl cellosolve, ethylene glycol butyl ether, methyl carbitol and ethyl carbitol; Ether-ether, for example methylcellosolve acetate and ethyl cellosolve acetate ， diox, dimethyl formamide, diacetone alcohol, methyl ethyl ketone, acetone, tetrahydrofurfuryl alcohol and composition thereof.
" ionogen " refers to the functional group on the polymkeric substance that can be dissociated into ionic species.The example of ionogen comprises-COOH ,-SO
3H ,-PO
4H
2And mixed group.
" neutralizing agent " refers to associate with the ionogen on the polymkeric substance and can be scattered in the component of the character of water with acquisition.The example that is used for neutralizing agent of the present invention comprises that the oxyhydroxide of amine, ammonia and metal comprises NaOH and KOH.In an importance of the present invention, neutralizing agent is amine and/or ammonia.
" linking agent " refers to that its functional group can form two or multifunctional material of covalent linkage with main or basic resin.
" linking agent that does not have significant quantity substantially " refers to that composition contains and is not higher than about 0.1% (weight) linking agent.Even aqueous dispersions of the present invention under the situation that does not have the significant quantity linking agent substantially, also can provide effective coating for polypropylene base.
Just as used herein, the reaction product of amine or ammonia and carboxyl forms " salt ".
" solvent-free substantially " refers to that polymer support or coatings formulated composition contain the organic solvent that is not higher than about 5% (weight).
" solvent " refers to organic solvent.
" organic solvent " refer to comprise and be not limited to the liquid of carbon and hydrogen, but the boiling point of described liquid is under an about normal atmosphere and is not higher than in about 150 ℃ scope.
" hydrophilic solvent " refers to that the solubleness in water is at least about the solvent of 5% (weight)." volatile organic compound " (VOCs) defined by the 40C.F.R.51.000 of EPA at federal regulations.
" the coatings formulated composition of baking " refers in a single day be higher than heating or baking under the temperature of outside temperature, and the preparation coating composition of best film performance just can be provided.
Refer to that about " dispersion " of polymer support, coatings formulated composition or its component composition must comprise a kind of liquid and can be by the detected dispersed particle of scattering of light.
Refer to that about " dissolving " of polymer support, coatings formulated composition or its component the dissolved material is not being present in the liquid by the particulate form greater than the particulate of individual molecule that scattering of light is measured.
" solvable " refers to partially or completely to be dissolved in the liquid or solid in a kind of liquid." solvable mixing " refers to that liquid has mutual solubility." suction " refers to that liquid can be miscible with water.
" acid number " refer to neutralize be present in 1 gram material for example the ionogen on the resin or with the milligram quantities of the required potassium hydroxide of this ionogen reaction.
" thermoplastic polymer carrier " be film forming coating adhesive agent use do not need crosslinked polymer support.
" thermosetting polymer carrier " be film forming coating adhesive agent use carry out irreversible crosslinked polymer support.
" emulsifying agent that does not contain significant quantity substantially " refers to contain the composition that is not higher than about 0.5% (weight) emulsifying agent, is benchmark with the resin solid.Aqueous dispersions of the present invention does not contain the emulsifying agent of significant quantity substantially.
" tensio-active agent that does not contain significant quantity substantially " refers to contain the composition that is not higher than about 0.5% (weight) tensio-active agent, is benchmark with the resin solid.Aqueous dispersions of the present invention does not contain the tensio-active agent of significant quantity substantially.
Just as used herein, " stable aqueous dispersions " speech refers to contain median size and is lower than about 15 microns resin and also can reversibly isolating dispersion liquid after 120 down about 2 weeks.
The method according to this invention, even azeotropic point surpasses 100 ℃, the scope of employed " processing temperature " also is extremely up to about 100 ℃ or higher from about envrionment temperature.
Overall process of the present invention can be described below generally speaking.
Synthetic resins → in and resin → formation dispersion liquid → remove solvent
Synthesizing of resin
According to this step of the present invention, the chlorinatedpolyolefins of acrylic acid or the like modification is synthetic in organic solvent.Organic solvent can be the mixture of hydrophilic organic solvent, hydrophobic nature organic solvent or wetting ability and hydrophobic nature organic solvent.In an importance of the present invention, organic solvent is a hydrophilic solvent.The hydrophilic solvent that is used for the present invention has the solubleness at least about 5% (weight) in water under processing temperature.In one aspect of the invention, wherein polymer formation if desired, before neutralization subsequently, can join hydrophilic solvent in the solution that contains polymkeric substance in the mixture of hydrophobic nature organic solvent or hydrophobic nature and hydrophilic organic solvent.
In an importance of the present invention, the chlorinatedpolyolefins polymkeric substance is by carrying out modification with the acrylic acid or the like grafting.The cl content that is used for the present invention's chlorinatedpolyolefins polymkeric substance is about 15-35% (weight) (is benchmark with polymer solids weight), and weight-average molecular weight is about 1,000-200, and 000, an importance, be about 10,000-100,000.Aspect this, the example of chlorinatedpolyolefins polymkeric substance comprises CP-343-1 (Eastman), CY-9122P (Hardlen), CP-164-1 (Eastman) and composition thereof of the present invention.
The acrylic acid or the like that is grafted on the chlorinatedpolyolefins can be preformed acrylic polymers.Aspect this, the weight-average molecular weight of preformed acrylic polymers is about 2000-2 1,000,000 of the present invention.In addition, acrylic monomer can grafting and is aggregated on the chlorinatedpolyolefins.Of the present invention aspect this, the grafting of acrylic monomer is effective to the grafted acrylic polymers that forms weight-average molecular weight and be about 2000-2 1,000,000.
In an importance of the present invention, acrylic acid or the like provides ionogen for the chlorinatedpolyolefins of acrylic acid or the like modification.Of the present invention aspect this, wherein-COOH is an ionogen, and acid number is about 10-250, and preferred acid number is about 40-80.In another aspect of this invention, wherein ionogen comprises-SO
3H, acid number can be low to moderate 5 approximately.
Being used for acrylic resin of the present invention can be any acrylic resin that above-mentioned scope acid number is provided for the chlorinatedpolyolefins of acrylic acid or the like modification effectively.Acrylic resin can be by unsaturated ethylene linkage carboxylic acid or its acid anhydride that the carboxyl with above-mentioned acid number is provided for resin, with acrylate or methacrylic ester and the monomeric multipolymer formation of desired other unsaturated ethylene linkages.The example of unsaturated ethylene linkage carboxylic acid or its acid anhydride comprises vinylformic acid, methacrylic acid, Ba Dousuan, toxilic acid, methylene-succinic acid, citraconic acid, maleic anhydride, itaconic anhydride and citraconic anhydride.The monomeric example of unsaturated ethylene linkage that contains the ionogen of non--COOH comprises acrylamido (2-methyl propane sulfonic acid), vinyl phosphonate and vinylbenzene sodium sulfate.The example of acrylate or methacrylic ester comprises (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) lauryl acrylate and (methyl) vinylformic acid n-octyl.(methyl) acrylate is acrylate and methacrylic ester.The monomeric example of other unsaturated ethylene linkages can comprise for example vinylbenzene, Vinyl toluene, vinyl cyanide or methacrylonitrile, and vinyl acetate monomer, for example vinyl-acetic ester, new n-nonanoic acid vinyl acetate, vinyl neodecanoate and new dodecylic acid vinyl acetate.The CPO of formed acrylic acid or the like modification solubleness in hydrophilic solvent under processing temperature is at least about 25% (weight).
The neutralization of resin
In an importance of the present invention, polymer salt is formed in the organic solvent in position, and water is mixed with polymer salt/ORGANIC SOLVENT MIXTURES.According to the present invention, neutralizing agent is joined in the organic solvent solution that contains resin, its add-on be in and the significant quantity of resin, purpose be form capacity salt so that resin can be scattered in the water.Being used for neutralizing agent of the present invention comprises and is not limited to ammonia, trolamine, dimethylethanolamine, diethylamine (DEA), triethylamine (TEA), 2-amino-2-methyl-1-propanol and composition thereof.
The add-on of neutralizing agent depends on chemical type, acid number and molecular weight.In one aspect, wherein ionogen is a carboxyl, in and the carboxyl of about 30-100%, obtain dispersion liquid of the present invention.
By make on the polymer belt ionogen for example-COOH ,-SO
3H ,-PO
4H
2And the salt of the metal of mixed group, amine or ammonia, just can the pre-neutralization polymkeric substance.Be not neutralized as yet if form the ionogen of the part of polymkeric substance, the polymkeric substance of being made by these " pre-neutralization " monomers is at least about 5 by the acid number that titration records so.
The formation of dispersion liquid
This method next step, water is added in the resin solution that is neutralized.The general temperature of water that adds is about 25-65 ℃.In an importance of the present invention, the initial ratio of solvent and water is about 3: 1-1: 3, one very important aspect, be about 1: 1.5.The add-on of water can be more than obtaining the needed amount of desired final dispersion liquid solid.During the solvent distillation, generally can lose some water.Add before the entry, the initial sufficient solvent that needs of system makes the salt dissolving.
In another aspect of the present invention, the polymkeric substance in the hydrophilic solvent is joined in the water that contains neutralizing agent.
Removing of solvent
This method next step, if desired, organic solvent and water are removed or stripping from the resin/water/solvent mixture that is neutralized.Can reduce pressure to mixture, helping to remove solvent and water, but also can be under without the situation of vacuum the stripping solvent.Under the situation of an employing vacuum of the present invention, vacuum range can be about the 10-35 inch of mercury.Temperature is low more, just must use high more vacuum removal solvent.In another kind of situation of the present invention, by using heat exchanger heat supply, stripping solvent/water.Use heat exchanger can shorten distillation time and reduce temperature, but also can make the destruction of salt reduce to minimum.
In an importance of the present invention,, can be obtained up to few about 10-50% (weight) solids content for the chlorinatedpolyolefins of acrylic acid or the like modification.One very important aspect, the solids content of dispersion liquid is at least about 25% (weight).
In another aspect of this invention, can also reuse the solvent that is removed by purifying.Simple flash distillation or multistep distillation are enough to remove the solvent of any pollution.
In yet another aspect, the present invention also can adopt a reaction vessel by the polymer manufacture aqueous dispersions.
Aqueous dispersions of the present invention does not need the emulsifying agent or the tensio-active agent of significant quantity, and after the solvent distillation, can not contain the organic solvent that is higher than about 10% (weight), is benchmark with the composition weight.An importance, aqueous dispersions contains the 0.2-3% that has an appointment (weight) organic solvent, one very important aspect, contain the organic solvent of have an appointment 2% (weight).In addition, aqueous dispersions of the present invention viscosity at ambient temperature is lower than 10 pools, of the present invention one very important aspect, the viscosity under the envrionment temperature is lower than about 1 pool.
Aqueous dispersions of the present invention comprises the polymer salt and the not salifiable polymkeric substance that can be scattered in the water, but in one aspect of the invention, wherein ionogen is a carboxyl, and aqueous dispersions of the present invention can not contain and is lower than 30% the free carboxyl group that is neutralized or transforms salifiable polymkeric substance.Because the acid number of polymkeric substance reduces, must in and the carboxyl of more high percent on the polymkeric substance.In ionogen be-situation of COOH under, in order to keep the dispersion liquid acid number about below 15, about 100% carboxyl on the polymkeric substance all should in and salify.In an importance of the present invention, about 100% carboxyl on the polymkeric substance all in and salify, and dispersion liquid of the present invention can not contain the VOC that is higher than about 2.5 pounds/gallon (300g/1), one very important aspect, dispersion liquid contains 0.5 pound of/gallon VOC that has an appointment.The present invention contains the aqueous dispersions of 0.5 pound of/gallon VOC that has an appointment through being still stable to circulating up to about 4 freeze-thaws at least about 1.Add a small amount of solvent or glycol, can improve the freeze-thaw number of cycles of process, as often doing in the latex system.
In an importance of the present invention, polymer support does not need the linking agent of significant quantity, can toast so that the coating adhesive agent of coating composition to be provided.Of the present invention aspect this and provide the coating adhesive agent of available linking agent in the above thermofixation of envrionment temperature aspect, the polymer support that contains aqueous dispersions of the present invention can provide and contain the coatings formulated composition that is lower than about 2.8 pounds of/gallon VOC.Polymer support also contains the polymkeric substance with above-mentioned molecular weight and the salt thereof that can be scattered in the water, does not only need, and does not have emulsifying agent, tensio-active agent and the coalescing agent of significant quantity substantially.
In another aspect of this invention, can use various linking agents, improve the chemical property of coating system.Linking agent comprises and is not limited to aziridine, carbodiimide, isocyanic ester, melamine and composition thereof.Can use aziridine and the carbodiimide of about 0.1-10%, be benchmark with the resin total solids of system.Can use the isocyanic ester of about 0.1-30%, be benchmark with the resin total solids of system.Can use the melamine of about 0-50%, be benchmark with the resin total solids of system.
In an importance of the present invention, aqueous dispersions can be effectively for coating provides the sticking power to polyolefin substrate at least about 4B that is recorded by ASTM method D3359, and an importance, it can provide the sticking power of about 5B effectively for coating.
The following examples have illustrated the method for the present invention of implementing, and to should be understood to be explanation to the scope of the invention that defines in the appended claims, rather than restriction.
Embodiment 1
Synthesizing of the CPO resin of acrylic acid or the like modification
1. the MEK solvent is weighed in 2 liters of round-bottomed flasks that protection of condenser, inflated with nitrogen and agitator be housed, and is heated to 80 ℃.
2. 406 gram CP 343-1 resins (Eastman Chemical) are under agitation joined among the MEK very fast dissolving.
3. 188 gram cyclohexyl methacrylates (CHMA), 113 gram methyl methacrylates (MNA), 179 gram lauryl methacrylate(LMA)s (LMA) and 114 being restrained methacrylic acids (MAA) weighs and mixes.
4. 10.0 gram initiators are crossed (oxygen) sad tert-butyl ester and join in the above-mentioned monomer mixture, stir the mixture that forms, then, join in the dropping funnel.
5. adopt dropping funnel in 3 hours, to be metered into reaction flask in the mixture of monomer and initiator then.
6. when monomer adds, restrained (oxygen) sad tert-butyl ester with 2.5 and joined in the reaction medium, reactant was reacted 3 hours again.
7. then, the cooling resin solution, and filter.Solids content is 33.6%.
Embodiment 2
The preparation of the CPO dispersion liquid of acrylic acid or the like modification
1. in 12 liters of round-bottomed flasks of agitator, condenser and thermopair are housed, 2425 materials that restrain embodiment 1 are heated to 60 ℃.
2. 83.2 grams, 18.9% solution of ammonium hydroxide is joined in the flask, with mixed with resin 15 minutes.
3. then, 2377 gram water were joined in the flask in 15 minutes, this mixture mixed 30 minutes then.
4. add receiving system, use aspirator, material in the flask is vacuumized, remove MEK.
5. when overhead product is water, end underpressure distillation, cooling mixture also filters.
The character of the CPO dispersion liquid of acrylic acid or the like modification:
NVM： 26.2％
Viscosity (RV#3@ 100RPM): 35 centipoises
pH： 7.85
Embodiment 3
The preparation that adds the coating of the CPO dispersion liquid that the acrylic acid or the like modification is arranged
1. following component is carried out pre-mixing:
Ethylene glycol butyl ether 73.06 grams
Tamol 165A 1.06 grams
Triton CF 10 1.54 grams
Ammonia 28% 6.62 gram
2. stir and slowly add following 4 kinds of components down:
Purple 14.99 grams of quinacridone (Quinaridone)
Carbon black 0.41 gram
Red oxide 16.69 grams
Titanium dioxide 2.04 grams
Mixture mixed 15 minutes well, and then the glass sphere with 1.5 millimeters of 40 grams ground 1 hour down at 5000 rev/mins.
3. after grinding, component and mixing below stirring adds down.
Water 48.80 grams
Matting agent 1 11.90 grams
Matting agent 2 5.11 grams
4. the dispersion liquid with 600 gram embodiment 2 joins in the autonomous container.Stir and in resin, slowly add said mixture down, whole blend mixing 15 minutes.
Can estimate that the technician in the industry has considered above-mentioned detailed description of the present invention, can carry out many improvement and variation to enforcement of the present invention.Therefore, these improvement and variation are contained in the scope of appended claims.
Claims (25)
1. aqueous polymer dispersion, it is made up of the neutral polymer salt in water substantially, wherein said polymkeric substance is the chlorinatedpolyolefins of acrylic acid or the like modification, the granularity of the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification in the dispersion liquid is not more than 15 microns, and be not equal to 1150nm, dispersion liquid contains the organic solvent that is lower than 10 weight %, the solid of at least 10 weight %, this dispersion liquid can form a kind of like this coating effectively: its viscosity at ambient temperature less than 10 the pool, do not contain the significant quantity emulsifying agent, polyolefin substrate is had the sticking power of 4B at least.
2. aqueous polymer dispersion as claimed in claim 1, the solution of the chlorinatedpolyolefins polymkeric substance of wherein said acrylic acid or the like modification is formed in the organic solvent, and the solubleness of wherein said polymkeric substance in organic solvent is at least 25 weight % under processing temperature.
3. aqueous polymer dispersion as claimed in claim 2, the chlorinatedpolyolefins of wherein said acrylic acid or the like modification is by forming with the acrylic acid or the like graft chlorinated polyolefin.
4. aqueous polymer dispersion as claimed in claim 3, wherein said chlorinatedpolyolefins contains the chlorine of 15-35 weight %, is benchmark with the weight of polymer solids, and its weight-average molecular weight is 1,000-200,000.
5. aqueous polymer dispersion as claimed in claim 3, the weight-average molecular weight of wherein said acrylic acid or the like is at least 2000, and it acid number is provided effectively is the chlorinatedpolyolefins of the acrylic acid or the like modification of 10-250.
6. aqueous polymer dispersion as claimed in claim 5, wherein said acrylic acid or the like are preformed acrylic polymerss.
7. aqueous polymer dispersion as claimed in claim 5, wherein said acrylic monomer grafting also is aggregated on the chlorinatedpolyolefins.
8. aqueous polymer dispersion as claimed in claim 2, the chlorinatedpolyolefins of wherein said acrylic acid or the like modification in organic solvent neutralizes with the neutralizing agent that is selected from ammonia, trolamine, dimethylethanolamine, diethylamine, triethylamine, 2-amino-2-methyl-1-propanol and composition thereof.
9. aqueous polymer dispersion as claimed in claim 2, wherein said dispersion liquid contains water, and described water joins in the neutral polymers soln, and add-on is for providing 3 effectively: 1-1: the initial ratio of 3 solvent and water.
10. aqueous polymer dispersion as claimed in claim 2, wherein said organic solvent is a hydrophilic organic solvent, its solubleness in water is at least 5 weight % under processing temperature.
11. one kind can be effectively as the aqueous dispersions of the chlorinatedpolyolefins polymkeric substance of the acrylic acid or the like modification of the coating of polyolefin substrate, this dispersion liquid is formed by the method that may further comprise the steps:
In organic solvent, form the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification, the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification has enough ionogens, so that form the chlorinatedpolyolefins polymkeric substance that acid number is at least 10 acrylic acid or the like modification, the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification forms like this: will have the acrylic monomer grafting of ionogen and be aggregated on the chlorinatedpolyolefins, and form the chlorinatedpolyolefins polyolefine of the acrylic acid or the like modification with acrylic acid or the like part;
The cl content of chlorinatedpolyolefins polymkeric substance is 15-35 weight %, weight with solid-state chlorinatedpolyolefins polymkeric substance is benchmark, and weight-average molecular weight is 1,000-200,000, the weight-average molecular weight of acrylic acid or the like part is 2,000-2,000,000, the solubleness of chlorinatedpolyolefins polymkeric substance in organic solvent of acrylic acid or the like modification is at least 25 weight % under processing temperature;
With form effectively the neutral polymers soln in and dosage, in and the ionogen of the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification;
The solution of neutral polymkeric substance is mixed with water, form the blend of neutral polymkeric substance, organic solvent and water; With
Under the temperature and pressure that forms such dispersion liquid effectively, from blend, remove organic solvent, the granularity of the chlorinatedpolyolefins polymkeric substance of the acrylic acid or the like modification of this dispersion liquid is not more than 15 microns, dispersion liquid contains the organic solvent that is lower than 10 weight %, the solid of at least 10 weight %, viscosity at ambient temperature is less than 10 pools, and this dispersion liquid can form effectively has the coating of the sticking power of 4B at least to polyolefin substrate; The granularity of described polymkeric substance is not equal to 1150nm.
12. aqueous polymer dispersion as claimed in claim 11, wherein said acrylic acid or the like are preformed acrylic polymerss.
13. aqueous polymer dispersion as claimed in claim 11, wherein said acrylic monomer grafting also is aggregated on the chlorinatedpolyolefins.
14. aqueous polymer dispersion as claimed in claim 11, wherein said ionogen be selected from-COOH ,-SO
3H ,-PO
4H
2And mixed group.
15. aqueous polymer dispersion as claimed in claim 11, the chlorinatedpolyolefins of the acrylic acid or the like modification in the wherein said organic solvent are selected from the neutralizing agent neutralization of ammonia, trolamine, dimethylethanolamine, diethylamine, triethylamine, 2-amino-2 methyl isophthalic acids-propyl alcohol and composition thereof.
16. aqueous polymer dispersion as claimed in claim 11, wherein said water is to provide 3 effectively: 1-1: the initial ratio of 3 solvent and water adds in the solution of neutral polymkeric substance.
17. aqueous polymer dispersion as claimed in claim 11, wherein said organic solvent is a hydrophilic organic solvent, and its solubleness in water under processing temperature is at least 5 weight %.
18. a method that forms the described aqueous polymer dispersion of claim 1, this method comprises the steps:
In organic solvent, form the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification, the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification has enough ionogens, so that form the chlorinatedpolyolefins polymkeric substance that acid number is at least 10 acrylic acid or the like modification, the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification forms like this: will have the acrylic monomer grafting of ionogen and be aggregated on the chlorinatedpolyolefins, and form the chlorinatedpolyolefins polyolefine of the acrylic acid or the like modification with acrylic acid or the like part;
The cl content of chlorinatedpolyolefins polymkeric substance is 15-35 weight %, weight with solid-state chlorinatedpolyolefins polymkeric substance is benchmark, and weight-average molecular weight is 1,000-200,000, the weight-average molecular weight of acrylic acid or the like part is 2,000-2,000,000, the solubleness of chlorinatedpolyolefins polymkeric substance in organic solvent of acrylic acid or the like modification is at least 25 weight % under processing temperature;
With form effectively the neutral polymers soln in and dosage, in and the ionogen of the chlorinatedpolyolefins polymkeric substance of acrylic acid or the like modification;
The solution of neutral polymkeric substance is mixed with water, form the blend of neutral polymkeric substance, organic solvent and water; With
Under the temperature and pressure that forms such dispersion liquid effectively, remove organic solvent from blend: the granularity of the chlorinatedpolyolefins polymkeric substance of the acrylic acid or the like modification of this dispersion liquid is not more than 15 microns, dispersion liquid contains the organic solvent that is lower than 10 weight %, the solid that contains at least 10 weight %, viscosity at ambient temperature is less than 10 pools, and this dispersion liquid can form effectively has the coating of the sticking power of 4B at least to polyolefin substrate.
19. method as claimed in claim 18, wherein said acrylic acid or the like are preformed acrylic polymerss.
20. method as claimed in claim 18, wherein said ionogen be selected from-COOH ,-SO
3H ,-PO
4H
2And mixed group.
21. method as claimed in claim 18, the chlorinatedpolyolefins of the acrylic acid or the like modification in the wherein said organic solvent are selected from the neutralizing agent neutralization of ammonia, trolamine, dimethylethanolamine, diethylamine, triethylamine, 2-amino-2-methyl-1-propanol and composition thereof.
22. method as claimed in claim 18, wherein said water is to provide 3 effectively: 1-1: the initial ratio of 3 solvent and water adds in the solution of neutral polymkeric substance.
23. method as claimed in claim 18, wherein said organic solvent is a hydrophilic organic solvent, and its solubleness in water under processing temperature is at least 5 weight %.
24. method as claimed in claim 18, wherein said acrylic acid or the like comprise the acrylic monomer that forms the acrylic acid or the like part.
25. method as claimed in claim 18, wherein said acrylic acid or the like are so preformed acrylic polymerss, it comprises acrylic monomer and is not the ethylenically unsaturated monomers of acrylic monomer.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16084398A | 1998-09-25 | 1998-09-25 | |
| US09/161,145 | 1998-09-25 | ||
| US09/161,145 US6277953B1 (en) | 1998-09-25 | 1998-09-25 | Stable aqueous polymer dispersions and a process for their preparation |
| US09/160,843 | 1998-09-25 | ||
| US09/268,279 | 1999-03-15 | ||
| US09/268,279 US6225402B1 (en) | 1998-09-25 | 1999-03-15 | Aqueous based dispersions for polyolefinic substrates |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1354768A CN1354768A (en) | 2002-06-19 |
| CN1258554C true CN1258554C (en) | 2006-06-07 |
Family
ID=27388521
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998165468A Expired - Fee Related CN1258554C (en) | 1998-09-25 | 1999-09-15 | Aqueous based dispersions of polyolefinic substrates |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1086163B1 (en) |
| JP (1) | JP2002525407A (en) |
| CN (1) | CN1258554C (en) |
| AT (1) | ATE380839T1 (en) |
| AU (1) | AU767743B2 (en) |
| BR (1) | BR9914072B1 (en) |
| CA (1) | CA2345325C (en) |
| CZ (1) | CZ20011085A3 (en) |
| ES (1) | ES2296409T3 (en) |
| WO (1) | WO2000018827A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6599980B2 (en) * | 2001-06-11 | 2003-07-29 | Toyota Technical Center, U.S.A., Inc. | Aqueous coating composition and coated article |
| JP2003055597A (en) * | 2001-08-17 | 2003-02-26 | Fujikura Kasei Co Ltd | Matt coating material composition |
| JP4873828B2 (en) * | 2003-04-18 | 2012-02-08 | ユニチカ株式会社 | Method for producing chlorinated polyolefin resin aqueous dispersion |
| CN102391430A (en) * | 2005-06-03 | 2012-03-28 | 三菱化学株式会社 | Aqueous resin dispersion, method for producing same, coating material, and multilayer body |
| WO2008064210A2 (en) * | 2006-11-21 | 2008-05-29 | Johnson Controls Technology Company | Flexible interior component |
| PL2094749T3 (en) * | 2006-12-07 | 2011-11-30 | Sherwin Williams Luxembourg Investment Man Company S A R L | Waterborne coating compositions |
| WO2009121889A1 (en) * | 2008-03-31 | 2009-10-08 | Dsm Ip Assets Bv | Coating composition comprising autoxidisable component |
| US10227487B2 (en) | 2014-12-08 | 2019-03-12 | Rohm And Haas Company | Polyolefin additive, a sag resistant polyolefin and a method of preparing the same |
| US10703830B2 (en) | 2014-12-08 | 2020-07-07 | Rohm And Haas Company | Process for preparing a (meth)acrylate additive, a method of improving the sag resistance of a polyolefin and a sag resistant polyolefin |
| CN105153841B (en) * | 2015-08-28 | 2017-11-03 | 东来涂料技术（上海）有限公司 | A kind of resistant chemicals-resistant aqueous automobile trim paint and preparation method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH086009B2 (en) * | 1988-04-06 | 1996-01-24 | 東洋化成工業株式会社 | Carboxylated polyolefin chlorinated emulsion |
| DE3910901A1 (en) * | 1989-04-04 | 1990-10-11 | Ppg Ind Deutschland Gmbh | METHOD FOR PRODUCING AN AQUEOUS PARTICULAR DISPERSION OF A CHLORINE POLYOLEFIN AND USE THEREOF IN AQUEOUS COATING COMPOSITIONS |
| JP2727032B2 (en) * | 1991-03-27 | 1998-03-11 | 東洋化成工業株式会社 | Method for producing resin composition emulsion |
| GB9112141D0 (en) * | 1991-06-05 | 1991-07-24 | Ici Resins Bv | Aqueous coating compositions |
| US5102946A (en) * | 1991-06-27 | 1992-04-07 | E. I. Du Pont De Nemours And Company | Stabilized chlorinated resin latex |
| JP3383980B2 (en) * | 1991-12-16 | 2003-03-10 | 大日本インキ化学工業株式会社 | Aqueous paint composition |
| US5491191A (en) * | 1992-04-06 | 1996-02-13 | E. I. Du Pont De Nemours And Company | Stable chlorosulfonated resin latex |
| JP2873151B2 (en) * | 1993-07-14 | 1999-03-24 | 本田技研工業株式会社 | Aqueous primer composition |
-
1999
- 1999-09-15 CN CNB998165468A patent/CN1258554C/en not_active Expired - Fee Related
- 1999-09-15 EP EP99948276A patent/EP1086163B1/en not_active Expired - Lifetime
- 1999-09-15 CA CA002345325A patent/CA2345325C/en not_active Expired - Fee Related
- 1999-09-15 BR BRPI9914072-1A patent/BR9914072B1/en not_active IP Right Cessation
- 1999-09-15 WO PCT/US1999/021387 patent/WO2000018827A1/en active IP Right Grant
- 1999-09-15 ES ES99948276T patent/ES2296409T3/en not_active Expired - Lifetime
- 1999-09-15 CZ CZ20011085A patent/CZ20011085A3/en unknown
- 1999-09-15 AU AU61488/99A patent/AU767743B2/en not_active Ceased
- 1999-09-15 AT AT99948276T patent/ATE380839T1/en not_active IP Right Cessation
- 1999-09-15 JP JP2000572281A patent/JP2002525407A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP1086163A4 (en) | 2003-01-08 |
| EP1086163B1 (en) | 2007-12-12 |
| AU6148899A (en) | 2000-04-17 |
| JP2002525407A (en) | 2002-08-13 |
| CN1354768A (en) | 2002-06-19 |
| EP1086163A1 (en) | 2001-03-28 |
| CZ20011085A3 (en) | 2002-03-13 |
| ATE380839T1 (en) | 2007-12-15 |
| BR9914072A (en) | 2002-06-18 |
| WO2000018827A1 (en) | 2000-04-06 |
| BR9914072B1 (en) | 2010-07-13 |
| ES2296409T3 (en) | 2008-04-16 |
| CA2345325C (en) | 2008-10-14 |
| AU767743B2 (en) | 2003-11-20 |
| CA2345325A1 (en) | 2000-04-06 |
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